The Gibbs free energy change (ΔG) and how it's related to reaction spontaneity and equilibrium.
When you hear the term “free energy,” what do you think of? Well, if you’re goofy like me, maybe a gas station giving away gas. Or, better yet, solar panels being used to power a household for free. There’s even a rock band from Philadelphia called Free Energy (confirming my longtime suspicion that many biology terms would make excellent names for rock bands).
These are not, however, the meanings of “free energy” that we’ll be discussing in this article. Instead, we’re going to look at the type of free energy that is associated with a particular chemical reaction, and which can provide a measure of how much usable energy is released (or consumed) when that reaction takes place.
A process will only happen spontaneously, without added energy, if it increases the entropy of the universe as a whole (or, in the limit of a reversible process, leaves it unchanged) – this is the Second Law of Thermodynamics. But to me at least, that's kind of an abstract idea. How can we make this idea more concrete and use it to figure out if a chemical reaction will take place?
Basically, we need some kind of metric that captures the effect of a reaction on the entropy of the universe, including both the reaction system and its surroundings. Conveniently, both of these factors are rolled into one convenient value called the Gibbs free energy.
The Gibbs free energy (G) of a system is a measure of the amount of usable energy (energy that can do work) in that system. The change in Gibbs free energy during a reaction provides useful information about the reaction's energetics and spontaneity (whether it can happen without added energy). We can write out a simple definition of the change in Gibbs free energy as:
In other words, ΔG is the change in free energy of a system as it goes from some initial state, such as all reactants, to some other, final state, such as all products. This value tells us the maximum usable energy released (or absorbed) in going from the initial to the final state. In addition, its sign (positive or negative) tells us whether a reaction will occur spontaneously, that is, without added energy.
When we work with Gibbs free energy, we have to make some assumptions, such as constant temperature and pressure; however, these conditions hold roughly true for cells and other living systems.
Gibbs free energy, enthalpy, and entropy
In a practical and frequently used form of Gibbs free energy change equation, ΔG is calculated from a set values that can be measured by scientists: the enthalpy and entropy changes of a reaction, together with the temperature at which the reaction takes place.
Let’s take a step back and look at each component of this equation.
- ∆H is the enthalpy change. Enthalpy in biology refers to energy stored in bonds, and the change in enthalpy is the difference in bond energies between the products and the reactants. A negative ∆H means heat is released in going from reactants to products, while a positive ∆H means heat is absorbed. (This interpretation of ∆H assumes constant pressure, which is a reasonable assumption inside a living cell).
- ∆S is the entropy change of the system during the reaction. If ∆S is positive, the system becomes more disordered during the reaction (for instance, when one large molecule splits into several smaller ones). If ∆S is negative, it means the system becomes more ordered.
- Temperature (T) determines the relative impacts of the ∆S and ∆H terms on the overall free energy change of the reaction. (The higher the temperature, the greater the impact of the ∆S term relative to the ∆H term.) Note that temperature needs to be in Kelvin (K) here for the equation to work properly.
Reactions with a negative ∆G release energy, which means that they can proceed without an energy input (are spontaneous). In contrast, reactions with a positive ∆G need an input of energy in order to take place (are non-spontaneous). As you can see from the equation above, both the enthalpy change and the entropy change contribute to the overall sign and value of ∆G. When a reaction releases heat (negative ∆H) or increases the entropy of the system, these factors make ∆G more negative. On the other hand, when a reaction absorbs heat or decreases the entropy of the system, these factors make ∆G more positive.
Chart showing how the signs of ∆H and ∆S affect reaction spontaneity. Reactions with a negative ∆H and positive ∆S are spontaneous at all temperatures. Reactions with a positive ∆H and negative ∆S are non-spontaneous at all temperatures. Reactions with a negative ∆H and negative ∆S are spontaneous at low temperatures, while reactions with a positive ∆H and positive ∆S are spontaneous at high temperatures.
By looking at ∆H and ∆S, we can tell whether a reaction will be spontaneous, non-spontaneous, or spontaneous only at certain temperatures. If a reaction both releases heat and increases entropy, it will always be spontaneous (have a negative ∆G), regardless of temperature. Similarly, a reaction that both absorbs heat and decreases entropy will be non-spontaneous (positive ∆G) at all temperatures. Some reactions, however, have a mix of favorable and unfavorable properties (releasing heat but decreasing entropy, or absorbing heat but increasing entropy). The ∆G and spontaneity of these reactions will depend on temperature, as summarized in the table at right.
Endergonic and exergonic reactions
Reactions that have a negative ∆G release free energy and are called exergonic reactions. (Handy mnemonic: EXergonic means energy is EXiting the system.) A negative ∆G means that the reactants, or initial state, have more free energy than the products, or final state. Exergonic reactions are also called spontaneous reactions, because they can occur without the addition of energy.
Reactions with a positive ∆G (∆G > 0), on the other hand, require an input of energy and are called endergonic reactions. In this case, the products, or final state, have more free energy than the reactants, or initial state. Endergonic reactions are non-spontaneous, meaning that energy must be added before they can proceed. You can think of endergonic reactions as storing some of the added energy in the higher-energy products they form.
It’s important to realize that the word spontaneous has a very specific meaning here: it means a reaction will take place without added energy, but it doesn't say anything about how quickly the reaction will happen. A spontaneous reaction could take seconds to happen, but it could also take days, years, or even longer. The rate of a reaction depends on the path it takes between starting and final states (the purple lines on the diagrams below), while spontaneity is only dependent on the starting and final states themselves. We'll explore reaction rates further when we look at activation energy.
Reaction coordinate diagrams for exergonic and endergonic reactions. In the exergonic reaction, the reactants are at a higher free energy level than the products (reaction goes energetically downhill). In the endergonic reaction reaction, the reactants are at a lower free energy level than the products (reaction goes energetically uphill).
Spontaneity of forward and reverse reactions
If a reaction is endergonic in one direction (e.g., converting products to reactants), then it must be exergonic in the other, and vice versa. As an example, let’s consider the synthesis and breakdown of the small molecule adenosine triphosphate (), which is the "energy currency" of the cell.
is made from adenosine diphosphate () and phosphate () according to the following equation:
This is an endergonic reaction, with ∆G = under standard conditions (meaning concentrations of all reactants and products, pressure, degrees , and of ). In the cells of your body, the energy needed to make is provided by the breakdown of fuel molecules, such as glucose, or by other reactions that are energy-releasing (exergonic).
The reverse process, the hydrolysis (water-mediated breakdown) of , is identical but with the reaction flipped backwards:
This is an exergonic reaction, and its ∆G is identical in magnitude and opposite in sign to that of the ATP synthesis reaction (∆G = under standard conditions). This relationship of same magnitude and opposite signs will always apply to the forward and backward reactions of a reversible process.
Non-standard conditions and chemical equilibrium
You may have noticed that in the above section, I was careful to mention that the ∆G values were calculated for a particular set of conditions known as standard conditions. The standard free energy change (∆Gº’) of a chemical reaction is the amount of energy released in the conversion of reactants to products under standard conditions. For biochemical reactions, standard conditions are generally defined as ( ), concentrations of all reactants and products, pressure, and of (the prime mark in ∆Gº’ indicates that is included in the definition).
The conditions inside a cell or organism can be very different from these standard conditions, so ∆G values for biological reactions in vivo may vary widely from their standard free energy change (∆Gº’) values. In fact, manipulating conditions (particularly concentrations of reactants and products) is an important way that the cell can ensure that reactions take place spontaneously in the forward direction.
To understand why this is the case, it’s useful to bring up the concept of chemical equilibrium. As a refresher on chemical equilibrium, let’s imagine that we start a reversible reaction with pure reactants (no product present at all). At first, the forward reaction will proceed rapidly, as there are lots of reactants that can be converted into products. The reverse reaction, in contrast, will not take place at all, as there are no products to turn back into reactants. As product accumulates, however, the reverse reaction will begin to happen more and more often.
This process will continue until the reaction system reaches a balance point, called chemical equilibrium, at which the forward and reverse reactions take place at the same rate. At this point, both reactions continue to occur, but the overall concentrations of products and reactants no longer change. Each reaction has its own unique, characteristic ratio of products to reactants at equilibrium.
When a reaction system is at equilibrium, it is in its lowest-energy state possible (has the least possible free energy). If a reaction is not at equilibrium, it will move spontaneously towards equilibrium, because this allows it to reach a lower-energy, more stable state. This may mean a net movement in the forward direction, converting reactants to products, or in the reverse direction, turning products back into reactants.
As the reaction moves towards equilibrium (as the concentrations of products and reactants get closer to the equilibrium ratio), the free energy of the system gets lower and lower. A reaction that is at equilibrium can no longer do any work, because the free energy of the system is as low as possible. Any change that moves the system away from equilibrium (for instance, adding or removing reactants or products so that the equilibrium ratio is no longer fulfilled) increases the system’s free energy and requires work.
How cells stay out of equilibrium
If a cell were an isolated system, its chemical reactions would reach equilibrium, which would not be a good thing. If a cell's reaction reached equilibrium, the cell would die because there would be no free energy left to perform the work needed to keep it alive.
Cells stay out of equilibrium by manipulating concentrations of reactants and products to keep their metabolic reactions running in the right direction. For instance:
- They may use energy to import reactant molecules (keeping them at a high concentration).
- They may use energy to export product molecules (keeping them at a low concentration).
- They may organize chemical reactions into metabolic pathways, in which one reaction "feeds" the next.Example of how a cell can keep reactions out of equilibrium. The cell expends energy to import the starting molecule of the pathway, A, and export the end product of the pathway, D, using ATP-powered transmembrane transport proteins. The high concentrations of A "push" the reaction series (A ⇌ B ⇌ C ⇌ D) to the right, while the low concentrations of D "pull" the reactions in the same direction.
Providing a high concentration of a reactant can "push" a chemical reaction in the direction of products (that is, make it run in the forward direction to reach equilibrium). The same is true of rapidly removing a product, but with the low product concentration "pulling" the reaction forward. In a metabolic pathway, reactions can "push" and "pull" each other because they are linked by shared intermediates: the product of one step is the reactant for the next.
Curious how this pushing and pulling actually works? Check out the reaction coupling video to learn more!
Want to join the conversation?
- Why is it that in Spontaneity of Forward and Reverse Reactions, the change in G for both the forward and reverse reactions is equal to +7.3 kcal/mol? Aren't the signs supposed to be opposite? And isn't the change in G supposed to be positive for endergonic and negative for exergonic? Wouldn't a positive change in G for an exergonic reaction go against the Laws of Gibbs Free Energy Change?(20 votes)
- I thought the same as you. Think it's an error. The second part of explanation (i.e. ATP + H2O -> ADP + Pi) is exergonic, so it should be -7.3kcal/mol(20 votes)
- Why is it called free energy instead of available energy?(19 votes)
- It is the amount of work a thermodynamic system can perform. It is free to do any work, i.e. the internal energy minus any energy that is unavailable to perform work.(14 votes)
- Is Gibbs Free Energy a type of potential energy?(5 votes)
- Nope! Gibb's free energy is the fancy name for a calculation that tells you if a reaction will go spontaneously, and if not, the amount of energy you'd need to put into a system to get that reaction to happen.(12 votes)
- What does Sal mean by the term "spontaneous"?
Is the scientific meaning different to the everyday meaning?(2 votes)
- In german we call this process 'unsolicited'. That means the process needs no specific catalyst or starting event to occur. It just happens by itself once the conditions are right.(13 votes)
- What is the definition of Gibbs Free Energy?(5 votes)
- "A thermodynamic quantity equal to the enthalpy (of a system or process) minus the product of the entropy and the absolute temperature."
named after J. W. Gibbs (see Gibbs, Josiah Willard).(2 votes)
- what is free energy(0 votes)
- free energy is energy that can do work when temperature and pressure are uniform, as in a living cell(3 votes)
- When the reaction is an endergonic one, does it mean that it will not happen? And do reactions which decrease entropy(with the change of entropy <0) increase the overall entropy of the surroundings and the universe? Thank you!(3 votes)
- When a reaction is endergonic, it means that the reaction will not happen spontaneously, but may happen if there were some changes in energy.
Reactions that decrease entropy, if spontaneous (meaning that if they are exothermic and happen at a low temperature), will increase the overall entropy of the universe because heat is released. This is because of the second law of thermodynamics, which states that the entropy of the universe increases with any spontaneous process.
Think of it like this: The universe includes both the system's disorder and the disorder of the surroundings. Thus, a spontaneous process can occur, in which the system becomes more ordered (meaning entropy decreases), only if the entropy increase in the surroundings is greater. For example, when ice freezes below 0 degrees Celcius, the liquid water goes to a more ordered solid state. That is, the system loses entropy. However, as the ice freezes, heat is given off the surroundings. This heat flow increases random motion of molecules in the surroundings and increases the entropy of the surroundings. So in the system, even though entropy decreases, the entropy of the surroundings and universe increase.
However, just to reiterate, this is only for reactions that are spontaneous. A non-spontaneous reaction that is decreasing the entropy of the system will decrease the entropy the universe because the reverse reaction is spontaneous (and will therefore increase the entropy of the universe).(3 votes)
- Is free energy useful energy that can do work and don't include the heat ? Because heat is not as useful like other energy ( potential energy in chemical bonds... )(3 votes)
- Heat can be useec to do work. For example, a steam engine can use heat energy in steam to move pistons. However, heat is transferred to the surroundings and so the general entropy is increased.
Some say that this release of heat will lead to the `heat death of the Universe', as there is no more general movement for the heat to go. Thus you are partly right.(3 votes)
- Is free energy kinetic or potential ?(2 votes)
- Free energy-"A thermodynamic quantity equivalent to the capacity of a system to do work." Since it says constant pressure and temperature and that Gibbs Free energy measures thermodynamic potential, it may be kinetic.(0 votes)
- How are gibbs free enrgy and equilbrium related to each other?(1 vote)